Effective Click Construction of Bridged- and Spiro-Multicyclic Polymer Topologies with Tailored Cyclic Prepolymers (kyklo-Telechelics)

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• 作者：Naoto Sugai ; Hiroyuki Heguri ; Kengo Ohta ; Qingyuan Meng ; Takuya Yamamoto ; Yasuyuki Tezuka
• 刊名：Journal of the American Chemical Society
• 出版年：2010
• 出版时间：October 27, 2010
• 年：2010
• 卷：132
• 期：42
• 页码：14790-14802
• 全文大小：547K
• 年卷期：v.132,no.42(October 27, 2010)
• ISSN：1520-5126

文摘

An alkyne−azide addition, i.e., click, reaction in conjunction with an electrostatic self-assembly and covalent fixation (ESA-CF) process has been demonstrated to effectively construct a variety of unprecedented multicyclic polymer topologies. A series of single cyclic poly(tetrahydrofuran), poly(THF), precursors having an alkyne group (Ia), an azide group (Ib), two alkyne groups at the opposite positions (Ic), and an alkyne group and an azide group at the opposite positions (Id) have been prepared by the ESA-CF process. Moreover, a bicyclic 8-shaped precursor having two alkyne groups at the opposite positions (Ie) was synthesized. The subsequent click reaction of Ia with linear (IIa) and three-armed star (IIb) telechelic precursors having azide groups has been performed to construct bridged-type two-way (IIIa) and three-way (IIIb) paddle-shaped polymer topologies, respectively. Likewise, spiro-type tandem tricyclic (IVa) and tetracyclic (IVb) topologies resulted from Ib/Ic and Ib/Ie, respectively. Furthermore, three types of multicyclic topologies that are composed of repeating ring (Va), alternating ring/linear (Vb), and alternating ring/star (Vc) units have been synthesized from Id, Ic/IIa, and Ic/IIb, respectively.